Method of producing hydrocarbons



March 15, 1932. R H ET'AL 1,850,022

METHOD OF PIODUCING HYDROCARBONS Filed May 23, 1931 Jmaruhn Hubben Patented Mar. 15, 1932 UNITED STTES PATENT orrica JOHANNES MARUHN, OF BEBLIN-FRIEDENAU, AND LUDWIG T'U'IBBE N, OF BERLIN- NICOLASSEE, GERMANY METHOD OF PRODUCING HYDROCABBONS Application filed May 23, 1931, Serial No. 539,548, and in Germany December 16, 1925.

This application forms a continuation in part of Serial No. 434,695 which has matured into Patent No. 1,807,122 on May 26, 19 31, the only added matter beyond the description in the parent application being found in the last half of the next to the last paragraph of the specification immediately preceding the claims.

It is known to initiate the chemical reaction between coal, solid and liquid hydrocarbonaceous substances and hydrogen, without the co-action of suitable catalysts, under a high pressure and at a suitably high temperature by employing a plurality of appa 5 ratus, such as pumps, compressors, heating tubes, autoclaves, and the like, connected with one another in series, and to carry out the process within a shorter or longer period for the purpose of obtaining hydrogenation 0 products, oils, and gases.

sembling that used with Diesel motors.

Now, the present invention consists in the use of a suitably designed compression space of a hydraulic compression device, for instance such as shown and described in the German patent-specification 350,619, in order to convert in that compression space, and in one, continuous procedure carbonaceous substances, for instance fine-coal, browncoal, pit-coal and coke, preliminarily dried and pulverized in known manner, or heavy oils, directly into distillable oils by introducing thestarting substance into said compression space, and adding hydrogen under high pressure, and at acorresponding temperature, without the co-action of a substance adapted to act as a catalyst.

A hydraulic press having a suitably de-' signed compression space is particularly useful for carrying out our improved meth od,that is to say, for employing solid hydrocarbons or heavy oils as starting materials and efl'ecting the known hydrogenating and splitting reactions in a direct way with out the insertion of special high-pressure apparatus or autoclaves into the path of the respective material.

As regards the hydrogenation of coal, this 7 process is carried out in the manner described iereinafter; which description is true also as regards heavy oils.

Using the compression space of a hydrauli c press renders possible without any difficulty the working of finely pulverized coal without any addition of oil, or turning the coal into a coal-oil-paste. There is attained o5 in'that space a direct and intimate mixture of the substances concerned and a reaction with hydrogen which can be carried out under a high pressure that may be regulated as desired, and at a temperature of any height;

catalysts are not used and the pressure used during that. period in which the reaction takes lace may be uniform or variable as desired or preferred.

a The difiicultyeoften experienced with the known hydrogenating processes of introducing the coal in unmixed state and in solid form into the high-pressure apparatus is done away with, as the hydraulic compression device permits the introduction of the pulverized coal into the pressing. space at a pressure of 1500 atm. and even higher, as is done with brown-coal briquetting machines. Besides said advantage, another advantage resides therein that, in contradis tinction to all known apparatus for the hydrogenation of coal, the employment of the hydraulic ress entails a considerable simplification o the process, and renders it cheaper. It must be borne in mind that the hydraulic press presents, for initiating and carrying outthe process, and above the known special highpressure compression plants, as used heretofore, the important technical, chemical, and economicaladvantages that the press we make meet is very compact, requires, therefore, only little space, and that the requisite devices and instruments for measuring the pressure and the temperature, for admittin the substances concerned, and for regulatin The results attained when operating ac-' cording to our invention depend, of course, as regards the quality of the product, upon the quality of the starting materials or substances, also upon the kind of the reduction agent used, but, on the other hand, they are independent of the process per se by reason of the new and particular employment of a technical ap aratus which can be used in connection withvall reaction agents, reaction :IGSSHIBS, and reaction temperatures that iave become known and have been used up to now. The object of the process per se is to obtain-in a simple manner distillable oils from solid hydrocarbons in the form of sufficiently, preliminarily dried and finely pulverized brown-coal or pit coal, as well as fine coal, and from heavy oils.

In experimental trials in which browncoal semi-coke was used as starting material there has been obtained, for instance, an amount of distillable oil equal to from 40 to in weight of that starting material, from 63 to 65% of that oil boiling at 280 0., 20% at a higher temperature, and the residue amounting to 17% having a softening po nt of 87 C. That'a part of the oxygen contained in the coal is converted into' water, another part is reduced to "the hydroxylgroup, that is to say, to phenols,.a part of 1 the often present sulphur is converted into ammonia, and finally, another part'is converted into gasiform hydrocarbons, all of which are known and comprehensible phenomena which do not impair the success of the direct production of distillable oils.

The hydraulic press for carrying out our improved process 'is illustrated diagrammatically and by way of example on the accompanying drawings in which Figure 1 is an axial section through the press, Figure 2 is a front view of the same, and Figure 3 is a detail, all as fully described hereinafter.

On the drawings, a is a cast-iron body and b a steel cylinder intowhich is inserted a working cylinder 0. The two cylinders can easily be removed from the body in order to be repaired etc., if necessary. Into the cylinder 6 is cast a coil d through which hot oil is to be conducted in order to heat the reaction mass contained in the cylinders. The plunger e which fits into the cylinder 0 has at its inner end or face a steel cup 2' which serves as a packing and tightening member for the plunger in the cylinder 0.

This cylinder 0 is designed as a sleeve in the cylinder 6, and this latter cylinder 6 is designed as a truncated cone at its closed end and is there provided with a passage ,1, aswell as with a transversely located slot can be shoved; the sectional-area of the passage 1 can be varied by said ledges which can be shoved towards, and away from one another and can form between them a gap of larger or smaller size, but the passage mentioned can also becompletely closed by said ledges, as will be obvious in view of theparticular shape of the ledges, as shown in Fig. 3. When that opening-is closed,- the reactlon mass can be'subjected to the requisite pressure which may amount to 1000 atm. and even more, and can be attained without particular pains and without any danger'for the apparatus.

In the cylinder 6 is passage m and in the bodya is a passage n, and a piece of tube 0 connects the two passages with a supply hopper 12. The tube 0 is-traversed by two slides h and i so that the material to'be fed into the cylinders 72 and a can be introduced in certain individual amounts corresponding to the space between said two slides and without bringing the interior of the cyhnders incommunication with the atmosphere.

The hydrogenating gas is supplied through thigaipe I: which terminates in the passage n.

pulverulent coal is used, the operation proceeds in this way that the hydrogenated mass is compressed by the plunger. e so much that space for the reception of another amount of the material and of the uisite amount of gas is provided, and the stroke of the plunger is so determined that the new or fresh amount is compressed only after the plunger has covered and closed the orifice of the passage m so that the hydrogen is prevented from escaping through' that passage. According to the present application, the reaction takes place gradually after the press plunger has reached its left end position (se eral minutes according to pressure, temperature, etc When the press plunger is tionary, the full pressure mustbe exerted.

during the said period on the material to be treated. It is obvious that a crank :press is by no means suitable for that purpose.

As regards the actuation of the press, we refer to the above-mentioned German patent-specification 350,619 in which matters are fully shown and described.

We claim:

A method of producing li uid hydrocarbons of low boiling point by ydrogenating and converting carbonaceous substances selected from a group comprising finely pulverized coal, heavy oilsand mixtures of pulverized coal and oil at an increased temperinto which two iron ledges f (Figs. 2nd 3) neeooee More and under nigh pressure of free hydro ell-containing gas; said. method consisting 1n feeding to a reaction zone e mixture of hydrogen-containing gas and said carbonuceous substances without a catalyst, heating and gradually compressing the mixture into a smaller volume in a, part of said zone until the maximum reaction PIQSSUZ'E of at least, 1000 atmospheres is reached, maintaining said maximum pressure several minutes and finally removing the product from said reactlon zone.

In testlmony whereof We afix our sleitures.

JOHANNES Peon. DR, LUDWIG T BEI L 

